Bonus Question #2 – CPA EOS Derivation 3 and 4 Sites – PETE 649 – Advanced Fluid Properties

Nur Iman Khamidy – 201703210 – PhD Student, PETE Dept, CPG, KFUPM

Case (3): Water with 3-Sites

The mole fraction of molecules NOT bonded at site A:

1 1
𝑋𝐴 = 𝐵 𝐴𝐵
=
1 + 𝑁𝐴𝑉 ∑𝐵 𝜌𝑋 ∆ 1 + 𝑁𝐴𝑉 𝜌𝑋 𝐶 ∆ 𝐴𝐶
The mole fraction of molecules NOT bonded at site B:
1 1
𝑋𝐵 = 𝐶 𝐵𝐶
=
1 + 𝑁𝐴𝑉 ∑𝐶 𝜌𝑋 ∆ 1 + 𝑁𝐴𝑉 𝜌𝑋 𝐶 ∆𝐵𝐶
The mole fraction of molecules NOT bonded at site C:
1 1
𝑋𝐶 = 𝐴 𝐶𝐴
=
1 + 𝑁𝐴𝑉 ∑𝐴 𝜌𝑋 ∆ 1 + 𝑁𝐴𝑉 𝜌𝑋 ∆ + 𝑁𝐴𝑉 𝜌𝑋𝐴 ∆𝐶𝐴
𝐵 𝐶𝐵

Since ∆ 𝐴𝐶 = ∆𝐵𝐶 = ∆𝐶𝐵 = ∆𝐶𝐴 = ∆, hence:

1 𝟏
𝑿 𝑨 = 𝑿𝑩 = ⇒ = 𝟏 + 𝑵𝑨𝑽 𝝆𝑿𝑪 ∆
1 + 𝑁𝐴𝑉 𝜌𝑋 𝐶 ∆ 𝑿𝑨

Then, plug in above relationship to 𝑋 𝐶 , therefore we can get:

1 1
𝑋𝐶 = 𝐴
⇒ 𝐶 = 1 + 2𝑁𝐴𝑉 𝜌𝑋 𝐴 ∆
1 + 2𝑁𝐴𝑉 𝜌𝑋 ∆ 𝑋

Find direct relationship between 𝑋 𝐴 and 𝑋 𝐶 :

1 2𝑋 𝐴 𝐶
2𝑋 𝐴 𝐴
2𝑋 𝐴 2
𝐴 ( 𝐶 ) = (1 + 𝑁𝐴𝑉 𝜌𝑋 ∆) ( 𝐶 ) ⇒ 2𝑁𝐴𝑉 𝜌𝑋 ∆= − 𝐶
+ 𝐶
𝑋 𝑋 𝑋 𝑋 𝑋

1 𝐴
2𝑋 𝐴 2
𝐶
= 1 + 2𝑁𝐴𝑉 𝜌𝑋 ∆= 1 − 𝐶
+ 𝐶 ⇒ 𝑿𝑪 = 𝟐𝑿𝑨 − 𝟏
𝑋 𝑋 𝑋
Bonus Question #2 – CPA EOS Derivation 3 and 4 Sites – PETE 649 – Advanced Fluid Properties
Nur Iman Khamidy – 201703210 – PhD Student, PETE Dept, CPG, KFUPM
1
Plug in 𝑋 𝐶 into 𝑋 𝐴 relationship, rearrange the equation, so we can get:

1
= 1 + 𝑁𝐴𝑉 𝜌(2𝑋 𝐴 − 1)∆ ⇒ 2𝑁𝐴𝑉 𝜌∆(𝑋 𝐴 )2 + (1 − 𝑁𝐴𝑉 𝜌∆)𝑋 𝐴 − 1 = 0
𝑋𝐴
Find the quadratic equation roots 𝑋 𝐴 from the following relationship below:

−(1 − 𝑁𝐴𝑉 𝜌∆) ± √(1 − 𝑁𝐴𝑉 𝜌∆)2 + 4(2𝑁𝐴𝑉 𝜌∆)

𝑋𝐴 =
2(2𝑁𝐴𝑉 𝜌∆)

−(𝟏 − 𝑵𝑨𝑽 𝝆∆) + √(𝟏 + 𝑵𝑨𝑽 𝝆∆)𝟐 + 𝟒𝑵𝑨𝑽 𝝆∆

∴ 𝑿𝑩 = 𝑿𝑨 =
𝟒𝑵𝑨𝑽 𝝆∆

−(1 − 𝑁𝐴𝑉 𝜌∆) + √(1 + 𝑁𝐴𝑉 𝜌∆)2 + 4𝑁𝐴𝑉 𝜌∆ 2𝑁𝐴𝑉 𝜌∆

𝑋 𝐶 = 2𝑋 𝐴 − 1 = 2 [ ]−
4𝑁𝐴𝑉 𝜌∆ 2𝑁𝐴𝑉 𝜌∆

−(𝟏 + 𝑵𝑨𝑽 𝝆∆) + √(𝟏 + 𝑵𝑨𝑽 𝝆∆)𝟐 + 𝟒𝑵𝑨𝑽 𝝆∆

∴ 𝑿𝑪 =
𝟐𝑵𝑨𝑽 𝝆∆
Bonus Question #2 – CPA EOS Derivation 3 and 4 Sites – PETE 649 – Advanced Fluid Properties
Nur Iman Khamidy – 201703210 – PhD Student, PETE Dept, CPG, KFUPM

Case (4): Water with 4-Sites

The mole fraction of molecules NOT bonded at site A:

1 1
𝑋𝐴 = 𝐵 𝐴𝐵
=
1 + 𝑁𝐴𝑉 ∑𝐵 𝜌𝑋 ∆ 1 + 𝑁𝐴𝑉 𝜌𝑋 ∆ + 𝑁𝐴𝑉 𝜌𝑋𝐷 ∆ 𝐴𝐷
𝐶 𝐴𝐶

The mole fraction of molecules NOT bonded at site B:

1 1
𝑋𝐵 = 𝐶 𝐵𝐶
=
1 + 𝑁𝐴𝑉 ∑𝐶 𝜌𝑋 ∆ 1 + 𝑁𝐴𝑉 𝜌𝑋 ∆ + 𝑁𝐴𝑉 𝜌𝑋𝐷 ∆𝐵𝐷
𝐶 𝐵𝐶

The mole fraction of molecules NOT bonded at site C:

1 1
𝑋𝐶 = 𝐷 𝐶𝐷
=
1 + 𝑁𝐴𝑉 ∑𝐷 𝜌𝑋 ∆ 1 + 𝑁𝐴𝑉 𝜌𝑋 ∆ + 𝑁𝐴𝑉 𝜌𝑋𝐴 ∆𝐶𝐴
𝐵 𝐶𝐵

The mole fraction of molecules NOT bonded at site D:

1 1
𝑋𝐷 = 𝐴 𝐷𝐴
=
∑
1 + 𝑁𝐴𝑉 𝐴 𝜌𝑋 ∆ 1 + 𝑁𝐴𝑉 𝜌𝑋 ∆ + 𝑁𝐴𝑉 𝜌𝑋𝐴 ∆𝐷𝐴
𝐵 𝐷𝐵

Since ∆ 𝐴𝐶 = ∆ 𝐴𝐷 = ∆𝐵𝐶 = ∆𝐵𝐷 = ∆𝐷𝐵 = ∆𝐶𝐵 = ∆𝐷𝐴 = ∆𝐶𝐴 = ∆, hence:

1
𝑋𝐷 = 𝑋𝐶 =
1 + 𝑁𝐴𝑉 𝜌𝑋𝐵 ∆ + 𝑁𝐴𝑉 𝜌𝑋𝐴 ∆
1 1
𝑋𝐵 = 𝑋 𝐴 = 𝐶
⇒ 𝑋𝐷 = 𝑋𝐶 =
1 + 2𝑁𝐴𝑉 𝜌𝑋 ∆ 1 + 2𝑁𝐴𝑉 𝜌𝑋𝐴 ∆
Substitute the relationship of 𝑋 𝐶 to 𝑋 𝐴 , we can get
1 1 1
𝑋𝐴 = = =
𝐶
1 + 2𝑁𝐴𝑉 𝜌𝑋 ∆ 1 + 2𝑁 𝜌 ( 1
𝐴𝑉 ) ∆ 1
1 + 2𝑁𝐴𝑉 𝜌𝑋𝐴 ∆ 1+( )
1⁄ 𝐴
(2𝑁𝐴𝑉 𝜌∆) + 𝑋
1⁄ 𝐴
(2𝑁𝐴𝑉 𝜌∆) + 𝑋
𝑋𝐴 = ⇒ 2𝑁𝐴𝑉 𝜌∆(𝑋 𝐴 )2 + 𝑋 𝐴 − 1 = 0
1⁄ 𝐴
(2𝑁𝐴𝑉 𝜌∆) + 𝑋 + 1
Bonus Question #2 – CPA EOS Derivation 3 and 4 Sites – PETE 649 – Advanced Fluid Properties
Nur Iman Khamidy – 201703210 – PhD Student, PETE Dept, CPG, KFUPM

Find the quadratic equation roots 𝑋 𝐴 from the following relationship below:

−1 ± √1 + 4(2𝑁𝐴𝑉 𝜌∆) −1 + √1 + 8𝑁𝐴𝑉 𝜌∆

𝑋𝐴 = =
2(2𝑁𝐴𝑉 𝜌∆) 4𝑁𝐴𝑉 𝜌∆

−𝟏 + √𝟏 + 𝟖𝑵𝑨𝑽 𝝆∆
∴ 𝑿𝑩 = 𝑿𝑨 =
𝟒𝑵𝑨𝑽 𝝆∆

Plug in to the 𝑋 𝐶 , we can get:

1 1 2
𝑋𝐶 = = =
1 + 2𝑁𝐴𝑉 𝜌𝑋𝐴 ∆ −1 + √1 + 8𝑁𝐴𝑉 𝜌∆ 1 + √1 + 8𝑁𝐴𝑉 𝜌∆
1 + 2𝑁𝐴𝑉 𝜌 ( 4𝑁𝐴𝑉 𝜌∆ )∆

2(1 − √1 + 8𝑁𝐴𝑉 𝜌∆) −1 + √1 + 8𝑁𝐴𝑉 𝜌∆

𝑋𝐶 = = = 𝑋𝐴
1 − (1 + 8𝑁𝐴𝑉 𝜌∆) 4𝑁𝐴𝑉 𝜌∆

−𝟏 + √𝟏 + 𝟖𝑵𝑨𝑽 𝝆∆
∴ 𝑿𝑫 = 𝑿𝑪 = 𝑿𝑩 = 𝑿𝑨 =
𝟒𝑵𝑨𝑽 𝝆∆